Water thinnable coating compositions from aminoethylated interpolymers

ABSTRACT

Water thinnable coating compositions are prepared by incorporating therein as the pigment binder an acidified aminoethylated copolymer having pendant amino-alkylate groups of the formula WHEREIN R1 and R2 are independently selected from the group consisting of hydrogen and lower alkyl radicals of one to four carbon atoms and the average value of n ranges from about 1.0 to 2.5 and wherein the copolymer before aminoethylation contains at least 3 percent by weight pendant -COOH groups. Water dispersant epoxy resin coating compositions are also disclosed.

United States Patent 1191 Martin et al. I

[451 March 6, 1973 WATER THINNABLE COATING COMPOSITIONS FROM AMINOETHYLATED INTERPOLYMERS Inventors: Patrick H. Martin, Lake Jackson; Russell T. McFadden, Freeport, both of Tex.

Assignee: The Dow Chemical Corporation,

Midland, Mich.

Filed: March 31, 1971 Appl. No.: 129,975

u.s. c1 ..260/33.2 EP, 260/296 HN,

260/29.6 NR, 260/334 EP Int. Cl. ..co8r 45/24, C08f45/34 Field of Search ..260/80.73, 86.1 N, 33.2 R, 260/29.6 NR

References Cited UNITED STATES PATENTS 1/1966 v5.1a ..l6l/l86 5/1968 l-lonig..... 3/1968 Fertig ..260/86.l N

3,321,451 5/1967 Gander ..260/80.73

Primary Examiner-Morris Liebman Assistant ExaminerP. R. Michl Attorney-Griswold & Burdick [5 7 ABSTRACT Water thinnable coating compositions are prepared by incorporating therein as the pigment binder an acidified aminoethylated copolymer having pendant amino-alkylate groups of the formula 7 Claims, No Drawings WATER TI-IINNABLE COATING COMPOSITIONS FROM AMINOETHYLATED INTERPOLYMERS BACKGROUND OF THE INVENTION Such compositions have generally exhibited problems either in application characteristics or in the poor appearance of the dried film. Consequently, enamel and other gloss coatings have continued to be deposited from oil systems. The disadvantages of oil coating systems are well known to anyone who has ever wielded a paint brush or roller. Not the least of those disadvantages is equipment, site and personal cleanup requiring liberal use of turpentine or similar odoriferous thinner. The widespread acceptance of aqueous coatings systems whenever available attests to their desirability in the minds of the painter.

Two package water dispersible epoxy coating compositions have been prepared employing polyamides as the curing agents. The coatings of the present invention exhibit better application properties such as faster tackfree drying properties and better coating properties such as better color, than do the coatings employing a polyamide as the curing agent.

SUMMARY OF THE INVENTION ing pendant amino alkylate groups of the formula wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals of one to four carbon atoms and the average value of n within the range of from about 1.0 to about 2.5, and wherein the interpolymer before aminoethylation contains at least about 3 percent and preferably more than 5 percent by weight pendant -COOH groups. The invention also contemplates the utilization of these acidified polymers in water miscible solvents in the formulation of a complete coating composition. The invention also contemplates the utilization of these acidified polymers in water dispersible epoxy resin coating compositions DETAILED DESCRIPTION OF THE INVENTION The aminoethylated interpolymers may be prepared according to methods disclosed in US. Ser. No. 840,795 filed July 10, 1969, by McFadden. In that disclosure it is taught that vinyl interpolymers containing pendant carboxyl groups may be prepared by the solution polymerization of a mixture of monomers one of which is a vinyl carboxylic acid monomer. The monomer mixture is polymerized in the presence of a catalyst and usually under controlled elevated temperatures with agitation until the polymerization reaction is complete. Various modifications commonly practiced with solution polymerization reactions can be utilized, modifications such as stepwise addition of the monomer mixture during the polymerization, incremental addition of catalyst, polymerization under an inert atmosphere, continuous or batch polymerization and the like. The details of such polymerization are well known and need not be discussed further herein.

The vinyl carboxylic acid monomers include the afiethylenically unsaturated monocarboxylic acids such as acrylic, metha'crylic, cinnamic, crotonic acids and the like; unsaturated dicarboxylic acids such as maleic, fumaric, itaconic acids and the like; half esters of the unsaturated dicarboxylic acids cited above and mixtures thereof. Preferably the vinyl carboxylic acids are unsaturated monocarboxylic acids and most preferred are acrylic and methyacrylic acid.

The vinyl interpolymer is prepared by copolymerizing a vinyl carboxylic acid with one or more copolymerizable monomers such as vinyl aromatic monomers, alkyl esters of unsaturated monocarboxylic acids, dialkyl esters of unsaturated dicarboxylic acids, vinyl and vinylidene chloride and fluoride, N -vinyl pyrrolidone and the like.

Suitable vinyl aromatic monomers include styrene, a-methylstyrene, vinyl toluene, the various alkyl substituted styrenes, the various halo substituted styrenes, vinyl naphthalene and the like. The more preferred of these monomers are styrene, a-methylstyrene and vinyl toluene. Suitable alkyl esters of unsaturated monoand dicarboxylic acids include the esters prepared from aliphatic alcohols containing from one to 12 carbon atoms and from cyclohexyl alcohol with the vinyl carboxylic acids cited previously. The acrylic and methacrylic esters are preferred; most preferred of these monomers are methyl, ethyl, isopropyl, butyl and Z-ethylhexyl 'acrylates or methacrylates. Small amounts of acrylonitrile, less than about 10 percent, may also be used to improve the film properties.

The interpolymers preferred herein are those of styrene with one or more acrylate or methacrylate monomers and the vinyl carboxylic acid. In one preferred subgenus the styrene may constitute up to 60 weight percent of the monomers that are interpolymerized with the remainder of the acrylic monomer and the acid. Equally preferred are those interpolymers employing up to weight percent of acrylic monomers.

The vinyl interpolymers are preferably prepared with a sufficient amount of vinyl carboxylic acid monomer to provide at least 3 percent and preferably from about 7.5 to about 12.5 percent by weight of carboxylic acid (as -COOH) and the balance of said interpolymer composed of the preferred comonomers as indicated above.

Suitable solvents for the polymerization include alcohols, ketones, aromatic hydrocarbons and the like or mixtures thereof. The polymerization temperature may range from 60 to 140C, with a preferred range of 80 to C. The particular temperature is variable depending on the monomers, the catalyst and other conditions.

The aminoethylated interpolymers employed in this invention are prepared by an amination reaction in which the vinyl carboxylic acid interpolymer in a suitable solvent is reacted with an excess of alkylenimine or an Ne(aminoalkyl) substituted alkylenimine. Suitable alkylenimines include the 1,2-alkylenimines such as ethylenimines such as ethyleriimine, propylenimine, butylenimine and the like and mixtures thereof. Ethylenimine is readily available in commercial quantities and is preferred. Particularly useful are the N- (aminoalkyl) substituted alkylenimines since they react similarly to the alkylenimines with a carboxylic acid group but are less volatile than the alkylenimines. Exemplary of these compounds are N-(2- aminoethyl)aziridine, N-(3-aminopropyl)aziridine, N- (2-aminopropyl)propylenimine, N-(2-aminobutyl)butylenimine and the like. Particularly preferred are N- (2-aminoethyl)aziridine and N-(2- aminopropyl)propylenimine.

To obtain a plurality of amine groups per carboxylic acid group, at least 2 moles of an alkylenimine per equivalent of carboxylic acid are reacted with the organic solvent solution of the vinyl carboxylic acid interpolymer in order to obtain an average 11 value, according to the formula, of at least 1.0. Preferably, the number of moles of alkylenimine ranges from about 2 to about 5 giving an average 11 value of about 1.5 to 2.5. With the N-(aminoalkyl)alkylenimine, at least one mole, and preferably 1 to 1.5 moles, per equivalent of carboxylic acid is used.

The temperature of the amination reaction is best conducted above about 50C. and preferably fromabout 50 to 100C, although higher temperatures and superatmospheric pressures'may be used. In contrast to these temperature conditions, the art suggests adding the imine at room temperature and keeping the temperature thereat for a period of time before heating the reaction mixture. The products produced thereby differ substantially in stability to the products of this invention and differ measurably in their amido nitrogen or unreacted acid content.

The. aminoethylated interpolymers may' also be prepared according to the teachings of Usala in US. Pat. No. 3,228,823 wherein from about 1 to about 2 moles of alkylene imine is added to the interpolymer containing pendant carboxyl groups at room temperature resulting in aminoethylated interpolymers having an average n value of from about 1 to about 1.3. The aminoethylated interpolymers prepared in this manner exhibit considerably less shelf stability than those prepared according to McFadden; however, if the polymer is to be formulated into a coating and applied The amination reaction may be run in a solvent containing less than 20 percent by weight alcohol with the balance of the solvent comprising aromatic hydrocarin a relatively short period of time, this presents no par- 5 ticular problem.

The reaction of the alkylenimine or the N-(amino-alkyl)alkylenimine with the carboxylic acid group is favored by nonprotic solvents such as ketones and aromatic hydrocarbons such as methyl ethyl ketone, xylene, toluene, ethylbenzene and the like, but a portion or all of the nonprotic solvent may be replaced by an alcohol. Suitable alcohols include aliphatic alcohols containing from two to five carbon atoms, lower alkylene glycols having from about one to about six carbon atoms, lower alkyl monoethers of ethylene and propylene glycols, diacetone alcohol and the like.

bon solvents. After completion of the amination reaction, the solvent composition may be adjusted by solvent stripping to comprise from 30 to 100 percent by weight of an alcohol solvent and from to 0 percent by weight of a nonprotic solvent, preferably a ketone or ether. Particularly preferred solvents include ethanol, propanol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol and the monomethyl ether of propylene glycol. The final product may have a polymer concentration from 1 to 60 percent by weight depending on the polymer solubility and the particular application.

The aminoethylated interpolymers are acidified by simple mixing of the interpolymer and acid in a suitable water miscible solvent of solvent blend. Among such solvents are the lower alkyl ethers of ethylene, propylene, dipropylene and like glycols representative of which are the butyl ether of propylene glycol, the ethyl ether of ethylene glycol, the propyl ether of diethylene glycol, and an isobutyl ether of mixed propylene glycols. Other solvents will be known.

The useful acids are those that will form an acid salt with the pendant amine moieties of the interpolymer. Preferably the acid should be volatile. Thus, typical of the preferred species are formic and acetic acids. The less volatile acids, such as glycolic acid, propionic acid, butyric acid and the like may be used but the water resistance of the resultant coating is impaired. Inorganic acids such as phosphoric acid may also be employed.

The acid may be used in an amount to neutralize all of the amine groups and may be employed in excess of that amount or less than that amount. The minimum level to be used is that which will impart water dispersibility to the acidified aminoethylated interpolymer.

The acidified polymers of this invention are utilizable as the pigment binder for coating compositions such as gloss enamels. Typically, such enamels will include the pigment binder, pigment, and a liquid dispersing medium. The enamels may also include other materials commonly employed in such compositions such as extender pigments, viscosity adjusting'agents, preservatives and the, like. In addition, the interpolymers of this invention may be used with epoxy resins to obtain cross-linked coatings exhibiting the desirable proper ties of such compositions. I

Water dispersible or thinnable epoxy resin coatings can be prepared by mixing the acidified amino-ethylated interpolymers and the water-soluble aliphatic alcohol and glycol ether solvents discussed above with the desired epoxy resin.

The water dispersible epoxy resin compositions of this invention may be conveniently formulated as two package or component systems wherein one package comprises the acidified aminoethylated polymer, water miscible solvents, water and if desired, pigments, leveling agents, antifoam agents and other modifiers and the second package or component comprises the epoxy resin and, if desired, suitable water miscible solvents. When it is desired to apply the coating to the desired substrate, the contents of the two packages are blended m. o 0 o CH1 H2 X X X X1 [1 X XX 10 wherein X and X, are independently selected from hydrogen, chlorine, bromine and a lower alkyl group having from about one to about four carbon atoms;

wherein R and R, are independently hydrogen, chlorine, bromine or a lower alkyl group having from about one to about four carbon atoms.

J L J:

wherein R, R, and R are independently hydrogen, an alkyl or haloalkyl group having from about one to about four carbon atoms and a, b and c are integers, the sum of which is an integer having an average value of from about 3 to about 40;

wherein A is a divalent radical selected from the group consisting of an alkylene group having from about one to about four carbon atoms, an alkylidene group having from about one to about four carbon atoms, a cycloalkylidene group,

wherein n,, n, and n are integers, the sum of which is an integer having an average value of from about 0 to about 4, X is a halogen, i.e., chlorine, bromine or iodine, and A is hydrogen or the group 65 V 0 independently hydrogen, chlorine or bromine and wherein n has an average value of from about 0 to about 15. and

wherein n and n are integers, the sum of which is an integer from about to about 4 and X is chlorine or bromine.

Other epoxy resins useful herein will be known to the skilled worker.

In addition to gloss and semi-gloss enamels the polymers may be employed in maintenance enamels, floor enamels, seamless flooring coatings, aircraft finishes, clear finishes and exterior house paint and trim enamels.

The coating compositions of this invention may be employed as formulated without pigments, or if colored coatings are desired, they may be added without detracting from the scope of the present invention.

Minor quantities of formulation additives such as levelers, antifoaming agents, other resinous materials, and the like may also be added to the compositions without detracting-from the scope of the present invention.

The concept of the present invention is illustrated in the following examples wherein all parts and percentages are by weight.

In the examples, the following definitions and test procedures were employed:

I. Gloss was determined visually and rated according to the scale wherein high gloss means high visual gloss;,moderate gloss" means slight visual gloss; and low gloss means nearly flat.

II. Odor was determined by smell duringpainting with high meaning very objectionable; moderate meaning slightly objectionable; and low meaning not objectionable.

III. Brushability was determined by the resistance to brushing during hand brush painting of a surface with difficult meaning severe resistance to brushing or severe drag; good meaning slight resistance to. brushing or slight to moderate drag; and excellent" meaning very slight resistance to brushing or no significant drag.

IV. Rolling was evaluated with a hand roller over a large surface with poor meaning a poor wet edge and sagging bubbles; good meaning a good wet edge and and appearance and no dripping of paint and excellent meaning the same good wet edge but with improved appearance.

V. Dry time was the time period until the film was dry enough to handle without paint transferring to the hand.

VI. Clean up was the difficulty in cleaning up the paint equipment in water wherein poor means the brush can not be cleaned out; good means that the 0 brush can be cleaned with slight effort and excellent means the brush cleaned out with very little effort.

VII. Water resistance refers to the resistance of the paint to a water spot test of minutes to 1 hour after periods of dry from 18 hours to 7 days.

VIII. Resin Solids Approximately 1 gm. of

polymer solution is accurately weighed into a tarred aluminum weighing pan and then heated at 150C. until the pan and contents reach a constant weight.

% resin solids (wt. of resinous residue X l00)/(wt. of solution) IX. Viscosity (25C.) Gardner The polymer solution is poured into a Class V 10.75 mm. I.D., R.P.C. viscosity tube until the meniscus is level with the lower calibration. A cork is inserted to the upper calibration and the tube in inverted in a 25C. chamber. After 40 minutes the tube is quickly inverted and the time required (average of three determinations) for the bubble to touch the cork is measured.

X. Amine Equivalent Weight A 4-5 gm. sample of solution is weighed into a polyethylene beaker and dissolved in 50 ml. of isoprop'anol. The solution is then titrated potentiometrically with 1.0 NHCI. The amine equivalent weight is [(wt. of sample) X resin solids) X l000]/[(meq. of

1.0 NI-ICI to end point)] XI. Amine Hydrogen Equivalent Weight A weighed sample of polymer solution is reacted with an excess of phenyl glycidyl ether (PGE) as a 5% solution in glycol monoethyl ether by refluxing for 1 hour. To the hot solution is added an aliquot of hydrochlorination reagent (35 ml. conc. HCI 250 ml. of pyridine and 750 ml. of glycol monoethyl ether) and the mixture is refluxed for 40 minutes more. After cooling the remaining pyridinium chloride is titrated with 0.2 NKOI-I in ethanol to a cresol red endpoint. The amine hydrogen equivalent weight is given by [(wt. of sample) X resin solids) X l000]/[(meq. of KOI-I) (meq. of PGE) (meqLof hydrochlorinating reagent)] EXAMPLE 1' A. Preparation of a Polyaminoacrylate Resin in a Water-soluble Solvent A S-Iiter glass reactor was fitted for stirring, temperature control, reflux, nitrogen purging, and continuous monomer addition. To it was charged 1650 grams of isopropanol, and with stirring this was heated to 8283 C. The following mixture was then added continuously over a 2 hour period: styrene, 298 grams; methyl methyacrylate, 297 grams; butyl acrylate, 297 grams; methacrylic acid, 105 grams; and azobis(isobu- .tyronitrile), 10.0 grams. The mixture was stirred at C. for 16 hours, then 2.50 grams of addition azobis(isobutyronitrile) was added and heating was continued for three more hours. At this time the solution contained 37.5 percent solids (calculated, 37.8 percent). Next, grams of ethylenimine was added to. the solution at 78-82C. over a 12 minute period.

.After it had been stirred at 80C. for an additional 1 /2 hours at 80C., the polyaminoethylated solution was heated to boiling and 755 grams of distillate was collected by means of a simple distillation head. The solution was diluted with 100 grams of ethyl acetate and cooled to 25C. It had the following properties.

% Solids 54.2 Viscosity, cps 2600 Appearance Clear, light yellow Amine equivalent weight 790 Amine hydrogen equivalent wt. 530 Residual ethylenimine, wt. 0.75

On the basis of the above data, the n value for the polyaminoacrylate ester was 1.75 where n is -O- CH2CH2NH H or, n is the average number of imine units reacted on each carboxyl group in the original polymer.

B. A paint was formulated with the following composition:

Polymer of A above 525 parts Glycolic Acid 76 parts Methyl ether of diethylene glycol 150 parts Titanium dioxide 300 parts n-Propyl alcohol 150 parts The formulation was thoroughly mixed and brushed on a wood surface. Gloss was rated high; odor-very low; brushability was difficult; water resistance for a minute spot after 2 days drying was good and for a 30 minute spot after 16 days drying was good. Clean up of the brush and paint equipment with water was good.

EXAMPLE 2 A. Preparation ofa Polyaminoacrylate Resin for Formulation as an Exterior Trim Enamel The following weights of reactants and solvents were used to prepare a copolymer as in Example 1: isopropanol, 1,495 grams; methyl methacrylate, 375 grams, butyl acrylate, 750 grams; methacrylic acid, 185 grams; azobis(isobutyronitrile), 1 3 grams; ethylenimine, 185 grams; and ethylene glycol monoethyl ether, 1,000 grams. During the distillation step, 1,900 milliliters of liquid was collected.

Solution Properties:

% Solids 58.0 Viscosity 3700 Appearance Clear, light yellow Amine equivalent weight 840 Amine hydrogen equivalent wt. 563 Residual ethylenimine, wt. 0.12

The calculated n value was 1.33.

B. An exterior trim enamel was formulated with the following composition Polymer of A 420 grams Formic acid 20 grams Methyl ether of dipropylene glycol 60 grams n-Propyl alcohol 200 grams Titanium dioxide 300 grams Anhydrous and particulate colloidal silica sold as The formulation was thoroughly mixed and brushed on an exterior wood surface. Leveling properties were considered excellent; gloss was rated high; water resistance for a 15 minute spot test after overnight drying showed a slight softening and clean up of thebrush with water was excellent.

EXAMPLE 3 A. In a 3 gallon glass reactor, the following mixture was polymerized in 3,600 grams of isopropanol: styrene, 1030 grams; methyl methacrylate, 1,025 grams; butyl acrylate, 1,030 grams; methacrylic acid, 460 grams; and azobis(isobutyronitrile), 29 grams. The polymerization was carried out at 82-84C. for 22 hours, then 460 grams of ethylenimine was added at 8l-82C. and heating was continued for 4 hours. 3,615 Grams of liquid was distilled, during which a mixture of 1,325 grams of propylene glycol monomethyl ether and 1,220 grams of n-propanol was added.

Solution Properties:

% Solids 60.5 Viscosity, cps 15,600 Appearance Clear, yellow Amine equivalent weight 906 Amine hydrogen equivalent wt. 566 Residual ethylenimine wt. 0.02

The calculated n value was 1.26.

B. A paint was formulated from the following composition:

Polymer of A 83.2 grams n-Propyl alcohol 72 grams Formic acid 3jgrams Titanium dioxide 50 grams Methyl ether of dipropylene glycol 10 grams The formulation was mixed and sprayed onto cold rolled steel. The coating exhibited high gloss, low odor and excellent adhesion to the steel. Clean up of equip-' ment with water was excellent.

EXAMPLE 4 A. Preparation of a Polyaminoacrylate Resin Containing Water and Formic Acid The following components were reacted essentially as in Example 3: isopropanol, 3,800 grams; butyl acrylate, 1,785 grams; methyl methacrylate, 1,785 grams; styrene, 1,785 grams; methacrylic acid, 800 grams; azobis(isobutyronitrile) 10.0 grams; and ethylenimine, 800 grams. The isopropanol was replaced with 2,000 grams of propylene glycol monomethyl ether and 2,000 grams of n-propanol', then the solution was further diluted with a mixture of 605 grams of 91 percent formic acid and 430 grams of water.

Solution Properties:

% Solids 55.5 Viscosity, cps 16,200. Appearance Clear, yellow Amine equivalent weight 1040 Amine hydrogen equivalent wt. 640

The calculated n value was 1.25. The polymer solution was completely miscible with water.

B. A paint was formulated from the following composition:

Part 1 Polymer of A 300 grams Monomethyl ether of dipropylene glycol 125 grams Monoethyl ether of ethylene glycol 50 grams Titanium dioxide 175 grams Chrome oxide green 100 grams Water 268 grams Anhydrous and particulate colloidal silica sold as Cab-O-Sil M- 30 grams Part 2 N-propylalcohol 80 grams Diglycidyl ether of bisphenol A (E.E.W.* 186-l92) 105 grams Monoisobutyl ether of a mixture of monoand dipropylene glycols (sold as Dowanol PlB-T) 30 grams "E.E.W.= Epoxy equivalent weight Part 1 was formulated by mixing the polymer, water, titanium dioxide and Cab-O-Sil in a Waring Blendor for 5 minutes. The remaining ingredients were then added. Part 2 was prepared by mixing the three ingredients. Parts 1 and 2 were blended just before use.

The resulting paint was brushed on the steel surface of a piece of mechanical equipmentwith excellent flow and final appearance. It had good brushability and clean up was fair. Gloss was medium and the coating had a moderate alcohol odor.

EXAMPLE 5 A. Preparation of a Polyaminoacrylate Resin Using an N-SubstitutedAziridine The following mixture was polymerized in ethyl alcohol at 75-80C. for 8 hours: butyl acrylate, 218 grams; methyl methacrylate, 150 grams; methacrylic acid, 50 grams; and azobis(isobutyronitrile), 4.18 grams. With the resulting polymer solution at 75C., 82 grams of N-ethyl aziridine was added and allowed to react for 2 l hours. During this time the solids content rose from 45.8 percent to 50.0 percent. The ethanol was distilled and replaced with 250 grams of propylene glycol monomethyl ether; The solution was then neutralized by adding 132 grams of a 50 percent solution of acetic acid in water. This rendered the solution fully water-soluble. The solution had an amine equivalent weight of 1,614 on a liquid basis.

B. A paint was formulated from the following composition:

Polymer of A 51 1 grams Monomethyl ether of dipropylene glycol 100 grams Monoethyl ether of ethylene glycol 25 grams Titanium dioxide 250 grams Zinc oxide 50 grams 2,3,5,6-Tetrachloro-4 methyl sulfonyl pyridine 5 grams The ingredients were mixed and the resulting paint brushed on the siding of a house. Brushability and leveling was excellent. The coating had moderate gloss with poor water resistance. Clean up in water was excellent.

EXAMPLE 6 A. Preparation of a Polyaminoacrylate Resin Using N(2-Aminoethyl)Aziridine The following mixture was polymerized at 8085C. for 8 hours in a mixture of 386 grams of propylene glycol monomethyl ether and 130 grams of dipropylene glycol monomethyl ether: butyl acrylate, 178 grams; methylmethacrylate, 178 grams; styrene, 178 grams; methacrylic acid, 80 grams; and azobis(isobutyronitrile), 10 grams. The resulting polymer solution was a thick, water-white syrup. To it, at 8085C., was added 84 grams of 98 percent pure N(2- aminoethyl)aziridine. The mixture was stirred for 3 hours at- C., and then had an amine equivalent weight of 790. With the solution still at 80C., a solution of grams of 91 percent formic acid and grams of water was added slowly and stirred in.

Solution Properties:

% Solids 50.0 Appearance Clear, colorless Amine equivalent weight 1090 Amine hydrogen equivalent wt. 702

The calculated n value was 1.30.

The above ingredients were. dispersed in a Waring Blendor and thereafter was added:

Polymer of A 100 grams n-Propyl alcohol 100 grams Water 268 grams Monoethyl ether of ethylene glycol 40 grams This was thoroughly mixed to complete formulation of'Part 1.

A Part 2 was prepared by mixing parts of the diglycidyl ether of bisphenol A (E.E.W. 186-192) and 30 parts of the monomethyl ether of propylene glycol.

Immediately before use, Parts 1 and 2 were blended to form a paint. This was brushed on a substratum with poor brushability and fair clean up in water.

EXAMPLE 7 A. Preparation of Polyaminoacrylate Resin The following mixture was polymerized at 90-100 C. for 3 1% hours in 500 grams of n-propanol: styrene, 230 grams; methyl methacrylate, 230 grams; butyl acrylate, 230 grams; methacrylic acid, grams and azobis(isobutyronitrile), 17. grams. At the end of this time the solution contained 61.7 percent solids or 98 percent of the calculated amount. The solution diluted with 220 grams of propylene glycol monomethyl ether, and with the solution at 80-84C. 155 grams of 99 percent pure N(2-aminoethyl)aziridine was added over a 20 minute period, followed by 100 grams of distilled water. The clear solution was stirred overnight at ambient temperature, and the next morning 100 grams of 91 percent formic acid and 84 grams of water were added and stirred in.

Solution Properties:

a Higher unctionality Solids 50 Appearance Clear, yellow Amine equivalent weight 672 Amine hydrogen equivalent weight 400 The calculated n value was 1.60.

B. A paint was formulated from the following composition. Part 1 was prepared by blending minutes on a Waring Blendor.

Polymer of A 200 grams Monomethyl ether of dipropylene glycol 25 grams Monoethyl ether of ethylene glycol 30 grams Water 200 grams Titanium dioxide 250 grams After blending there was added:

Water 200 grams Polymer of A 150 grams Monoethyl ether of ethylene glycol 30 grams lsopropyl alcohol 30 grams Part 2 was prepared by mixing Diglycidyl ether of bisphenol A (E.E.W.

186-192) 120 grams Monoethyl ether of ethylene glycol 30 grams lsopropyl alcohol 20 grams Just before use, the paint was made by blendingParts l and 2. The paint was brushed on a surface with good brushability. The resulting coating had high gloss and low odor. Drying time was about 30 minutes. Clean up in water was excellent.

The monomer/catalyst mixture was added to the npropanol at 80C. over a 43 minute period. The temperature rose to 103C. due to the exothermic polymerization. The mixture was stirred at 90 for 3 hours more, and then contained 58.2 percent solids. It was cooled to 80 and'the ethylene glycol, ethyl ether was added. Then the aminoethyl aziridine was added dropwise at 80C. over a 30 minute period, then 100 grams water were added and stirred overnight to cool. The next morning the formic acid and 400 grams of distilled water were added.

B. Part 1 of a composition was prepared by dispersing the following ingredients for 5 minutes in a Waring Blendor.

Polymer of A l grams Water 150 grams Titanium dioxide 300 grams Aromatic 100 solvent 5 grams Chrome oxide green 30 grams EXAMPLE 8 A. Recipe:

N-propanol 500 grams Styrene 200 grams Butyl acrylate 200 grams Methyl methacrylate 200 grams Methacrylic acid 200 grams Azobis(isobutyronitrile) 16 grams Z-Aminoethylaziridine 200. grams Monoethyl ether of ethylene glycol 190 grams Water 500 grams 88% Formic acid 130 grams Anhydrous and particulate colloidal silica sold as Cab-O-Sil M-S l0 grams Thereafter was added:

Polymer of A 200 grams Water 250 grams Propylene glycol 100 grams Part 2 consisted of 210 grams of a liquid diglycidyl ether of bisphenol A (epoxy equivalent weight 189 and a viscosity of about 12,500 cps at 25C.).

Just before use, the paint was made by blending Parts 1 and 2. The resulting composition was brushed and rolled on a wall surface with good brushability and excellent roll properties. Drying time was 16 hours and exhibited excellent wet edge. The dried coating showed medium gloss, low odor and had excellent hardness and appearance. Clean up in water was excellent.

Gardner Color 3 Calculated n value was 1.6]

The viscosity of the composition was reduced with water and at 25 percent nonvolatiles had a Gardner viscosity of seconds; at 20 percent nonvolatiles a viscosity of 25 seconds; and at 18 percent nonvolatiles a viscosity of about 5 seconds.

B. A semi-gloss enamel was formulated from the polymer of A by forming a pigment dispersion of a Waring Blendor form.

Polymer from A l 15 grams Water 150 grams Titanium dioxide rutile 300 grams Anhydrous and particulate colloidal silica sold as Cab-O-Sil M-5 10 grams After dispersion, 5 grams of a slow evaporating organic solvent sold as Aromatic solvent was added to reduce the foam. Then 233 grams of polymer from A, 275 grams water and 50 grams propylene glycol were added.

A Part 2 was formed by mixing 200 grams of the diglycidyl ether of bisphenol A and 10 grams of the monomethyl ether of propylene glycol.

Just before use, Part 2 was added to the pigment dispersion and stirred until uniformly mixed.

The enamel was applied on aluminum panels with a solution was cooled. 605 Grams of 90 percent formic number 60 wire wound rod and baked for 15 minutes at acid was added, and the solution was bottled. 275F. Spot tests with various chemicals were run and evaluated after 15 minutes exposure. No effect on the Solids 55.0 cooling was seen with xylene, tetrahydrofuran, glacial 5 Xlffgig .3; acetic acid or percent sodium hydroxide. A slight Amine hydrogen equiv. Wt. 590 softening was seen with methyl ethyl ketone. Immersion of a coated panel in Skydrol, a hydraulic fluid used Calculated n 1.3 3 for airplanes, for 24 hours showed no affect on the 10 B. Part 1 of a formulation was prepared by blending: coating.

Coated panels which had been air dried for 1 week polymer of A 326 grams without baking showed excellent abrasion resistance Titanium dixide 150 grams n-Propyl alcohol 1 l0 grams when scratched with a fingernail. 1 10 grams The enamel was painted on dry wall board and the Chrome oxide green 100 grams coating subjected to a 5 minute spot test with various chemicals. Resistance was excellent with water, acetic 2 was made y mixing:

acid, 5 percent caustic, xylene and methyl ethyl ketone.

The coatings were smeared with crayon, pen, pencil s y y eihflofbisphenol lipstick and heel marks. Clean up in each instance was fisi' m' j gfggfg grams excellent. glycol 30.2 grams The application properties of the enamel showed 6015mm slight to moderate brush drag; roller application was excellent, the wet edge was adequate to roller coat a Parts 1 and 2 blended to form a palm The typical bedroom, the coating was tack free in about 2 ty as a g .1 i g f f to hours. Leveling was excellent. The coating had a low 0 s z or d l odor. Clean up in water was excellent. The enamel ex- 6 palm was Spraye on a ace an gave e.xce hibited apackage stability ofabout2 days. lent gloss when dry. Water resistance for a 5 minute Coatings of various proportions of the diglycidyl spot test after6days drying was slightly softened. Clean ether of -bisphenol A to lOO parts of part 1 were water was excellent prepared. These were coated on aluminum panels with EXAMPLE 1 1 a number 60 wire wound rod and baked for 15 minutes Y at 275F. The coated panels were exposed for 5 Rec'pei minutes to methyl ethyl ketone and to tetrahydrofuran. Other panels were bent around a mandrel. Reverse im- 'f g fs pact tests were run on other panels. The results are in a acryme 0 grams the following table. Methyl methacrylate 180 grams Parts Per Hundred Parts of Polymer A 6MEK softened softened" softened No effect" No effect" N0I t 0 0C 6"lIIF. (lo "do do l0 "do Do. Mandrel Fair 0K OK 0K ()K 0K. Reversoimpact.. Fail20 Pass 40.... lass 80.... Pass 40.. Fall 20 FailQU.

' i I Methacrylic acid 80 grams EXAMPLE l0 Azobisfisobutyronitrile) 10 grams A R Ethylenimine 80 grams p Monomethyl ether of dipropylene glycol 250 grams lsopmpanol 3800 grams 5O 91% Formlc acid water 43 grams Butyl acrylate 1785 grams h. 'tjigi l {32 Themonomer/catalyst mixture was polymerized for Meth acrylic d goo grams '20 hours at 80C. in the n-propanol, giving a solution Q containing 45.6 percent solids. The ethylenimine was Ethylemmme 800 grams 0 Pm we mm: added at 80 and digested for 2 hours, giving 46.6 perrnetir lemer' I 2215 grams cent solids. The dipropylene glycolzmonomethyl ether n-Propanol 2215 grams was added and 565 grams of n-propanol were distilled. The solution was cooled and the water and formic acid The i-propanol was brought to 80C. and the were stirred'm monomer/catalyst solution was added in 1,000 gram lots each hour. The polymer solution was stirred over- Solids 5 53 night at 80C., and then contained 59.9 percent SOlldS- Amine equivalent int. 850 With the solution at -80C., the ethylenimine was Amine hydrogen 552 added over a A hour period, and the solution was Calculatedn=l 57 stirred for two hours more at C., at which time it 65 B. A paint was prepared by blending Parts I and 2 contained 62.6 percent solids. The propylene glycol: identified as follows:

methyl ether was added and 4,000 grams of liquid was Part 1 was made by dispersing the following indistilled. Then the n-propanol was stirred in and the gredients for5 minutes in aWaring Blendor.

Polymer of A 300 grams Monomethyl ether of propylene glycol lOO grams n-Propyl alcohol 70 grams Water 268 grams Titanium dioxide 275 grams Part 2 was prepared by mixing 105 grams of the diglycidyl ether of bisphenol A 186-192) and 30 grams of the monomethyl ether of propylene glycol.

The parts were blended just prior to use and the paint brushed on a surface with good brushability. Drying time was fair. The coating had excellent gloss, very low odor and the hardness after several days air dry was excellent. Clean up in water was excellent.

In like manner, the benefits of the invention are obtained with other polymers containing up to 60 weight percent styrene and up to 20 weight percent of acrylic or methyacrylic acid with the remainder of a lower alkyl acrylate. A similarresult obtains when the interpolymer is one of up to 90 weight percent of an alkyl acrylate with the remainder of a vinyl carboxylic acid.

What is claimed is:

1. A water thinnable coating composition comprising (1) a water miscible solvent, (2) an acidified aminoethylated vinyl polymer dissolved in said solvent, said interpolymer having pendant aminoethyl groups of the formula wherein R and R are independently selected from the group consisting of hydrogen and lower alkyl radicals of one to four carbon atoms and the average value of n ranges from about 1.0 to about 2.5 and wherein the interpolymer before aminoethylation contains at least 3 percent by weight pendant -COOH groups and further wherein said aminoethyl groups are reacted with sufficient acid to impart water solubility to said interpolymer and (3) an epoxy resin.

2. The composition of claim 1 wherein the average value of n is from about 1.5 to about 2.5.

3. The composition of claim 1 wherein the interpolymer before aminoethylation contains from about 5 to about 15 percent by weight pendant --COOH groups.

4. The composition of claim 1 wherein the water miscible solvent is selected from the group consisting of aliphatic alcohols having from about one to about six carbon atoms, glycols, glycol monoethers and mixtures thereof.

5. The composition of claim 1 wherein said epoxy resin is a glycidyl ether of a polyhydric compound.

6. The composition of claim 5 wherein the polyhydric compound is a bisphenol.

7. The composition of claim 6 wherein the bisphenol is bisphenol A. 

1. A water thinnable coating composition comprising (1) a water miscible solvent, (2) an acidified aminoethylated vinyl polymer dissolved in said solvent, said interpolymer having pendant aminoethyl groups of the formula wherein R1 and R2 are independently selected from the group consisting of hydrogen and lower alkyl radicals of one to four carbon atoms and the average value of n ranges from about 1.0 to about 2.5 and wherein the interpolymer before aminoethylation contains at least 3 percent by weight pendant -COOH groups and further wherein said aminoethyl groups are reacted with sufficient acid to impart water solubility to said interpolymer and (3) an epoxy resin.
 2. The composition of claim 1 wherein the average value of n is from about 1.5 to about 2.5.
 3. The composition of claim 1 wherein the interpolymer before aminoethylation contains from about 5 to about 15 percent by weight pendant -COOH groups.
 4. The composition of claim 1 wherein the water miscible solvent is selected from the group consisting of aliphatic alcohols having from about one to about six carbon atoms, glycols, glycol monoethers and mixtures thereof.
 5. The composition of claim 1 wherein said epoxy resin is a glycidyl ether of a polyhydric compound.
 6. The composition of claim 5 wherein the polyhydric compound is a bisphenol. 